Polymer self-assembly is of considerable interest for the preparation of well-defined structures and materials. While polymer materials in solution are most commonly polydisperse random-coils, advances in polymer synthesis, supramolecular assembly, and interfacial segregation have generated polymer-based materials with structural features that possess unprecedented precision. When polymer assemblies contain reactive functionality, opportunities arise for crosslinking, and thus structural solidification, to give materials with wide applicability in both materials science and medicine.
An increased understanding of materials at a system or phase interface offers tremendous opportunities with regard to surfaces, thin films, and nano-structured materials. Amphiphilic polymers are particularly useful for mediation of the oil-water interface, as demonstrated by their rich science and commercial utility as polymer surfactants. Amphiphilic block copolymers are very interesting in this regard, as the range of accessible chemistries and molecular weights, for example in amphiphilic diblock copolymers, leads to polymer assemblies, micelles, and vesicles of considerable interest for encapsulation and controlled release.
The synthesis of amphiphilic graft copolymers has been the subject of on-going research, as the graft copolymer structure can be used to integrate into the polymer backbone functionality for subsequent chemical modification. Particular interest has been afforded copolymers of hydrophobic polyolefin backbones with covalently bound hydrophilic poly(ethylene glycol) (PEG) pendant chains, the preparation of which can be achieved by ring-opening metathesis copolymerization of cyclooctene and PEG-substituted cyclooctene macromonomers. The resulting PEGylated polycyclooctene copolymers can be designed or tuned as desired in terms of their backbone composition and graft molecular weight. In addition, a variety of grafted functionality and linker chemistry is accessible. However, the study of such compounds has not been extended to polymeric architectures and the interfacial assemblies thereof.